EP0963383A4 - CROSSLINKING OF THERMOPLASTIC ELASTOMERS BY HYDROSILYLATION - Google Patents
CROSSLINKING OF THERMOPLASTIC ELASTOMERS BY HYDROSILYLATIONInfo
- Publication number
- EP0963383A4 EP0963383A4 EP19980907618 EP98907618A EP0963383A4 EP 0963383 A4 EP0963383 A4 EP 0963383A4 EP 19980907618 EP19980907618 EP 19980907618 EP 98907618 A EP98907618 A EP 98907618A EP 0963383 A4 EP0963383 A4 EP 0963383A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- rubber
- elastomeric polymer
- weight percent
- composition
- hydrosilylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 32
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 29
- 238000004132 cross linking Methods 0.000 title abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 86
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 150000001993 dienes Chemical class 0.000 claims abstract description 22
- 230000006872 improvement Effects 0.000 claims abstract description 5
- 239000005060 rubber Substances 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 23
- 229920005992 thermoplastic resin Polymers 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 21
- 238000004073 vulcanization Methods 0.000 claims description 21
- -1 polypropylene Polymers 0.000 claims description 20
- 239000004711 α-olefin Substances 0.000 claims description 14
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 239000004606 Fillers/Extenders Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 2
- 239000000806 elastomer Substances 0.000 abstract description 11
- 230000000704 physical effect Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000306 component Substances 0.000 description 28
- 239000003921 oil Substances 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 18
- 238000002156 mixing Methods 0.000 description 11
- 229920001169 thermoplastic Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 235000001508 sulfur Nutrition 0.000 description 9
- 239000004416 thermosoftening plastic Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000001374 small-angle light scattering Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910052990 silicon hydride Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 101100497923 Viola odorata Voc1 gene Proteins 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920006258 high performance thermoplastic Polymers 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- MUUXBTFQEXVEEI-UHFFFAOYSA-N [2-(dimethyl-$l^{3}-silanyl)phenyl]-dimethylsilicon Chemical compound C[Si](C)C1=CC=CC=C1[Si](C)C MUUXBTFQEXVEEI-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- LDKSTCHEYCNPDS-UHFFFAOYSA-L carbon monoxide;dichloroplatinum Chemical compound O=C=[Pt](Cl)(Cl)=C=O LDKSTCHEYCNPDS-UHFFFAOYSA-L 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 239000003060 catalysis inhibitor Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- XAFJSPPHVXDRIE-UHFFFAOYSA-N dichloroplatinum;triphenylphosphanium Chemical compound Cl[Pt]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 XAFJSPPHVXDRIE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011545 laboratory measurement Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
Definitions
- thermoplastic elastomer compositions prepared using hydrosilylation crosslinking of the elastomer component of the composition.
- a thermoplastic elastomer is generally defined as a polymer or blend of polymers that can be processed and recycled in the same way as a conventional thermoplastic material, yet has properties and functional performance similar to that of vulcanized rubber at service temperatures. Blends or alloys of plastic and elastomeric rubber have become increasingly important in the production of high performance thermoplastic elastomers, particularly for the replacement of thermoset rubbers in various applications.
- High performance thermoplastic elastomers in which a highly vulcanized rubbery polymer is intimately dispersed in a thermoplastic matrix are generally known as thermoplastic vulcanizates.
- Polymer blends which have a combination of both thermoplastic and elastic properties are generally obtained by combining a thermoplastic resin with an elastomeric composition in a way such that the elastomer component is intimately and uniformly dispersed as a discrete particulate phase within a continuous phase of the thermoplastic.
- vulcanized rubber components include both static vulcanization of the rubber, as well as the technique of dynamic vulcanization wherein a vulcanizable elastomer is dispersed into a molten resinous thermoplastic polymer and the elastomer is cured while continuously mixing and shearing the blend.
- the resulting composition is a micro-gel dispersion of cured elastomer in an uncured matrix of thermoplastic polymer.
- U.S. Pat. No. 4,803,244 generally discusses the use of multifunctional organosilicon compounds in conjunction with a catalyst as an agent for crosslinking the rubber component of a thermoplastic elastomer by hydrosilylation.
- Hydrosilylation involves the addition of a silicon o hydride across a multiple bond, often with a transition metal catalyst.
- This patent describes a rhodium catalyzed hydrosilylation of EPDM rubber in a blend with polypropylene to produce thermoplastic elastomers having a gel content of up to 34% (after correction for the plastic phase). This degree of vulcanization was achieved only with a high level of catalyst.
- the present invention is based on the discovery that the process for hydrosilylation crosslinking of the rubber in a thermoplastic elastomer can be improved by employing as the rubber an ethylene, ⁇ -olefin, non-conjugated diene elastomeric polymer containing vinyl norbornene as a diene component. More particularly, it has been discovered that when the
- Mooney viscosity, ethylene content and diene content of this rubber are within defined ranges, unexpectedly low concentrations of hydrosilylation agent and catalyst will fully crosslink the rubber in the dynamic vulcanization process and provide a thermoplastic elastomer product with excellent physical properties and oil resistance.
- the ethylene, ⁇ -olefin, non-conjugated diene elastomeric polymer of the invention on which the blends with thermoplastic resins are based will generally have lower levels of diene to achieve similar or improved properties, when compared to blends made from previously available ethylene, ⁇ 0 -olefin, non-conjugated diene elastomeric polymers.
- the previously available elastomers contained a diene selected from 5-ethylidene-2-norbornene, 1 ,4-hexadiene, dicyclopentadiene, or combinations thereof and compounds derived from them.
- the combination of lower diene content and lower catalyst required lead to even better properties for heat aging, UV stability and colorability
- compositions produced by the improved process have utility as replacements for thermoset rubber compounds in a variety of applications, particularly where molding or extrusion is involved and the combination of thermoplastic and elastomeric properties provides an advantage.
- Typical uses include molded articles for automobile underhood parts, engineering and construction materials, mechanical rubber goods, industrial parts such as hose, tubing and gaskets, electrical applications and household goods.
- Thermoplastic elastomer compositions may generally be prepared by blending a thermoplastic resin and a rubber, then melting the thermoplastic component and mixing the melt until the blend is homogeneous. If a composition of vulcanized rubber in a thermoplastic matrix is desired, crosslinking agents (also referred to as curatives or vulcanizing agents) are added to the blend and crosslinking occurs during the mixing under conditions of heat and shear. This latter process is described as dynamic vulcanization.
- thermoplastic resins and/or their mixtures have been used in the preparation of thermoplastic elastomers, including polypropylene, polypropylene copolymers, HDPE, LDPENLDPE, LLDPE, polyethylene copolymers, cyclic olefin homopolymers or copolymers as well as olefinic block copolymers, polystyrene, polyphenylene sulfide, polyphenylene oxide and ethylene propylene copolymer (EP) thermoplastics.
- Thermoplastic resins useful in the compositions produced by the invention include crystalline and semi-crystalline polyolefin homopolymers and copolymers. They are desirably prepared from monoolefin monomers having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene and the like, as well as copolymers derived from linear and cyclic olefins, with propylene being preferred.
- polypropylene includes homopolymers of propylene as well as reactor copolymers of polypropylene which can contain about 1 to about 20 wt% of ethylene or an ⁇ -olefin comonomer of 4 to 20 carbon atoms, and mixtures thereof.
- the polypropylene can be atactic, isotactic or syndiotactic, made with
- thermoplastic resins which are substantially inert to the rubber, the silicon hydride and the hydrosilylation catalyst would also be suitable. Blends of thermoplastic resins may also be used.
- the amount of thermoplastic resin found to provide useful compositions is generally from about 5 to about 90 weight percent, based on the weight of the rubber and resin.
- the thermoplastic resin content will range from about 20 to about 80 percent by weight of the total polymer.
- an ethylene, ⁇ -olefin, non-conjugated diene elastomeric polymer containing vinyl norbornene as a diene component is used as the rubber component. It contains from about 40 to about 85 weight percent ethylene, preferably about 45 to about 80 weight percent, and more preferably in the range of from about 50 to about 75 weight percent.
- the rubber component contains in the range of from about 0.25 to about 5 weight percent of diene, preferably from about 0.25 to about 2 weight percent and more preferably in the range of from about 0.5 to about 1.2 weight percent.
- the balance of the ethylene, ⁇ -olefin, non-conjugated diene elastomeric polymer will generally be made up of an ⁇ -olefin selected from propylene,
- the elastomeric polymer has a Mooney viscosity, measured without oil in the polymer using ASTM D1646 with a small thin rotor (Mooney small thin - MST), generally in the MST (5+4) , 200°C range of from about 45 to about 100, preferably in the range of from about 50 to about 90 and most preferably in the range of about 50 to about 85.
- Mooney small thin - MST small thin rotor
- the polymer will have a branching index (BI) generally in the range of from about 0.1 to about 1.0, preferably in the range of from about 0.3 to about 1.0, and more preferably in the range of from about 0.5 to about 1.0.
- the elastomeric polymer will have a MwGPC, LALLS/MnGPC,DRI below about 20, preferably below about 10 and more preferably below about 8.
- the amount of rubber generally ranges from about 95 to about 10 weight percent, based on the weight of the rubber and thermoplastic resin.
- the rubber content will be in the range of from about 80 to about 20 weight percent of total polymer.
- the Ziegler polymerization of the double bond in vinyl norbornene is believed to produce a highly branched ethylene, ⁇ -olefin, vinyl norbornene elastomeric polymer.
- This method of branching permits the production of such elastomeric polymers substantially free of gel which would normally be associated with cationically branched ethylene, ⁇ -olefin, non-conjugated diene elastomeric polymer containing, for instance, a non-conjugated diene selected from the group consisting of 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene and the like.
- ENB 5-ethylidene-2-norbornene
- the catalysts used are VC1 4 (vanadium tetrachloride) and VOCl : , (vanadium oxytrichloride) with the latter as the preferred catalyst.
- the co-catalyst is chosen from (i) ethyl aluminum sesqui chloride (SESQUI), (ii) diethyl aluminum chloride (DEAC) and (iii) a 4/1 molar mixture of diethyl aluminum chloride to triethyl aluminum (TEAL). SESQUI is the preferred co-catalyst.
- the polymerization is carried out in a continuous stirred tank reactor at 20-65° C at a residence time of 6- 15 minutes at a pressure of 7 kg/cm 2 .
- the molar concentration of vanadium to alkyl is from 1 to 4 to 1 to 10. About 0.3 to 1.5 kg of polymer is produced per gram of catalyst fed to the reactor. The polymer concentration in the hexane solvent is in the range of 3-7% by weight.
- Other catalysts and co-catalysts may be used, some of which are disclosed in U.S. Pat. No. 5,153,282.
- This catalyst system includes Group IV transition metal compounds and compounds capable of activating these compounds to an active catalyst state.
- Suitable activators include the ionizing noncoordinating anion precursor and alumoxane activating compounds, both well known and described in the field of metallocene catalysis.
- an active, ionic catalyst composition comprising a cation of a Group IV transition metal compound and a noncoordinating anion result upon reaction of the Group IV transition metal compound with the ionizing noncoordinating anion precursor.
- the activation reaction is suitable whether the anion precursor ionizes the metallocene, typically by abstraction of R, or R 2 , by any methods inclusive of protonation, ammonium or carbonium salt ionization, metal cation ionization or Lewis acid ionization.
- the critical feature of this activation is cationization of the Group IV transition metal compound and its ionic stabilization by a resulting o compatible, noncoordinating, or weakly coordinating (included in the term noncoordinating) anion capable of displacement by the copolymerizable monomers.
- a resulting o compatible, noncoordinating, or weakly coordinating (included in the term noncoordinating) anion capable of displacement by the copolymerizable monomers See, for example, EP-A 0 277 003, EP-A 0 277 004, U.S. Pat. No. 5,198,401, U.S. Pat. No. 5,241,025, U.S. Pat. No.
- the inherent viscosity measured in decalin at 135° C was in the range of 2-6 dl/g.
- the molecular weight distribution (M w LALLS /M n GPC/DR1 ) was > 4.
- the branching index was in the range 0.3-0.7.
- Branching in ethylene, ⁇ -olefin, diene monomer polymers is quantified using a branching index factor. Calculating this factor requires a series of three laboratory measurements of polymer properties in solution. These are: (i) weight average molecular weight measured using low angle light scattering (LALLS) technique; (ii) weight average molecular weight and inherent viscosity using a differential refractive index detector (DRI); and (iii) inherent viscosity (IV) measured in decalin at 135° C. The first two measurements are obtained in a GPC using a 0 filtered dilute solution of the polymer in trichlorobenzene. An average branching index is defined as:
- Hydrosilylation has been disclosed as a crosslinking method.
- a silicon hydride having at least two SiH groups in the molecule is reacted with the carbon-carbon multiple bonds of the unsaturated (i.e. containing at least one carbon-carbon double bond) rubber component of the thermoplastic elastomer, in the presence of the thermoplastic resin and a hydrosilylation catalyst.
- Silicon hydride compounds useful in the process of the invention include methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers, methylhydrogen alkyl methyl polysiloxanes, bis(dimethylsilyl)alkanes and bis(dimethylsilyl)benzene.
- the amount of silicon hydride compound useful in the process of the present invention can range from about 0.1 to about 10.0 mole equivalents of SiH per carbon-carbon double bond in the rubber, and preferably is in the range of about 0.5 to about 5.0 mole equivalents of SiH per carbon-carbon double bond in the rubber component of the thermoplastic elastomer.
- any catalyst, or catalyst precursor capable of generating a catalyst in situ, which will catalyze the hydrosilylation reaction with the carbon-carbon bonds of the rubber can be used.
- Such catalysts have included transition metals of Group VIII such as palladium, rhodium, platinum and the like, including complexes of these metals.
- Chloroplatinic acid has been disclosed as a useful catalyst in U.S. Pat. No. 4,803,244 and U. S. Pat. No. 5,597,867, which further disclose that the catalyst may be used at concentrations of 5 to 10,000 parts per million by weight and 100 to 200,000 parts per million by weight based on the weight of rubber, respectively.
- These catalysts include chloroplatinic acid, chloroplatinic acid hexahydrate, complexes of chloroplatinic acid with sym-divinyltetramethyldisiloxane, dichloro-bis(triphenylphosphine) platinum (II), cis-dichloro-bis(acetonitrile) platinum (II), dicarbonyldichloroplatinum (II), platinum chloride and platinum oxide.
- Zero valent platinum metal complexes such as Karstedt's catalyst are particularly preferred, as described in U.S. Pat. No. 3,775,452; U.S. Pat. No. 3,814,730; and U.S. Pat. No. 4,288,345 all of which are incorporated herein by this reference.
- the thermoplastic elastomer may contain conventional additives, which can be introduced into the composition in the thermoplastic resin, the rubber, or in the blend either before, during or after the hydrosilylation and curing.
- additives are antioxidants, processing aids, reinforcing and nonreinforcing fillers, pigments, waxes, rubber processing oil, extender oils, antiblocking agents, antistatic agents, ultraviolet stabilizers, plasticizers (including esters), foaming agents, flame retardants and other processing aids known to the rubber compounding art.
- additives may comprise from about 0.1 to about 300 percent by weight based on the weight of the final thermoplastic elastomer product.
- Fillers and extenders which can be utilized include conventional inorganics such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black and the like. Additives, fillers or other compounds which may interfere with the hydrosilylation should be added after curing reaches the desired level.
- the rubber processing or extender oils used in thermoplastic elastomers generally are paraffinic, naphthenic or aromatic oils derived from petroleum fractions.
- the type will be that ordinarily used in conjunction with the specific rubber or rubbers present in the composition, and the quantity based on the total rubber content of the thermoplastic elastomer may range from zero to several hundred parts per hundred rubber.
- the oils and other additives contain no or very low concentrations of compounds that are catalyst inhibitors or that interfere with the activity of the catalyst. These compounds include phosphines, amines, sulfides, thiols or other compounds that may be classified as Lewis bases.
- Lewis bases or other compounds that have a pair of electrons available for donation, will react with the platinum catalyst, effectively neutralizing its activity. It has been discovered that the presence of such compounds has a surprisingly detrimental impact on hydrosilylation curing in the process of dynamic vulcanization of the rubber component of the thermoplastic elastomer compositions.
- the concentration of compounds which have the chemical reactivity of Lewis bases such as compounds containing sulfur or nitrogen
- the amount of platinum catalyst required to promote efficient hydrosilylation curing in dynamic vulcanization can be substantially reduced, usually to the range of about 4 ppm or less, without impact on the cure state of the rubber or the tensile properties of the thermoplastic elastomer product.
- Concentrations of sulfur and nitrogen below about 500 and 200 ppm respectively are more preferred, and concentrations of less than about 30 ppm sulfur and less than about 100 ppm nitrogen are most preferred.
- White and paraffinic oils have been treated more extensively than aromatic and napthenic oils and would contain a smaller concentration of aromatic, sulfur and/or nitrogen compounds. It is difficult to elucidate the exact chemical structure of these compounds due to their complexity.
- the tendency of an oil to interfere with platinum catalyzed hydrosilylation is directly related to the concentration of sulfur and nitrogen containing compounds, as well as compounds which contain phosphorus, tin, arsenic, aluminum and iron.
- the rubber component of the thermoplastic vulcanizate is generally present as small, i.e. micro-size, particles within a continuous thermoplastic resin matrix, although a co-continuous morphology or a phase inversion is also possible depending upon the amount of rubber relative to plastic and the degree of cure of the rubber.
- the rubber is desirably at least partially crosslinked, and preferably is completely or fully crosslinked. It is preferred that the rubber be crosslinked by the process of dynamic vulcanization.
- dynamic vulcanization means a vulcanization or curing process for a rubber blended with a thermoplastic resin, wherein the rubber is vulcanized under conditions of shear at a temperature at which the mixture will flow.
- Dynamic vulcanization is effected by mixing the thermoplastic elastomer components at elevated temperatures in conventional mixing equipment such as roll mills, Banbury mixers, Brabender mixers, continuous mixers, mixing extruders and the like.
- the unique characteristic of dynamically cured compositions is that, notwithstanding the fact that the rubber component is partially or fully cured, the compositions can be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding and compression molding. Scrap or flashing can be salvaged and reprocessed.
- corrected initial and final weights are obtained by subtracting from the initial weight the weight of soluble components, other than rubber to be vulcanized, such as extender oils, plasticizers and components of the composition soluble in organic solvent, as well as that rubber component of the product which is not intended to be cured. Any insoluble polyolefins, pigments, fillers, and the like are subtracted from both the initial and final weights.
- the rubber component can be described as fully cured when less than about 5%, and preferably less than 3%, of the rubber which is capable of being cured by hydrosilylation is extractable from the thermoplastic elastomer product by a solvent for that rubber. Alternatively the degree of cure may be expressed in terms of crosslink density. All of these descriptions are well known in the art, for example in U.S. Pat. Nos. 4,593,062, 5,100,947 and 5,157,081, all of which are fully incorporated herein by this reference.
- thermoplastic elastomers by the process of the invention, as set forth in the examples.
- the thermoplastic resin and oil extended rubber were placed in a heated internal mixer, with the hydrosilylation agent and hydrosilylation catalyst.
- the hydrosilylation agent and catalyst can be incorporated into the composition by any suitable technique, for example by injection as solutions in oil or as neat components, although a dilute catalyst solution is preferred.
- Additives such as antioxidants, ultraviolet stabilizers " and fillers may also be added as a slurry in oil. Masterbatches of the components may also be prepared to facilitate the blending process.
- the mixture was heated to a temperature sufficient to melt the thermoplastic component, and the mixture was masticated* with added processing oil if desired, until a maximum of mixing torque indicated that vulcanization had occurred. Mixing was continued until the desired degree of vulcanization was achieved.
- composition expressed as weight percent The remaining monomer is propylene.
- compositions were prepared as generally described above using polypropylene resin and EPDM rubber containing vinyl norbornene as a diene monomer.
- a masterbatch composition was prepared containing 100 parts rubber, 100 parts paraffinic extender oil, 42 parts clay (Icecap K) and 41 parts polypropylene. This blend was mixed in a Brabender mixer at 180 C until the polypropylene was melted. Silicone hydride (3 phr) was added dropwise to the mix, followed by addition of an oil solution containing platinum catalyst at various levels. The rubber was dynamically vulcanized by mixing the blend until maximum torque was reached. Additional processing oil was added after the cure. The product was removed from the mixer, then returned to the mixer and masticated at 180 C for an additional minute. Test specimens were prepared by compression molding the products at 200 C, and physical properties were determined. The results are set forth in the following table. TABLE
- Examples 1-4 are outside the scope of the invention.
- MST Mooney viscosity
- Examples 2-4 the diene content of the elastomeric polymer was below the critical level
- Example .1 the physical properties of the thermoplastic elastomer were inferior to the physical properties of compositions within the scope of the invention.
- the tensile strength of the products was low and the oil swell was high, indicative of a low degree of crosslinking of the rubber component.
- examples within the scope of the invention demonstrate that use of a rubber component containing about 0.3 weight percent or more of vinyl norbornene and having a Mooney viscosity in the MST range of from about 45 to about 100 produces a thermoplastic o elastomer product which has an unexpectedly improved combination of physical properties. This improvement is achieved even at extremely low concentrations of hydrosilylation catalyst.
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Applications Claiming Priority (3)
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US3943397P | 1997-02-26 | 1997-02-26 | |
US39433P | 1997-02-26 | ||
PCT/US1998/003645 WO1998038226A1 (en) | 1997-02-26 | 1998-02-25 | Hydrosilylation cross-linking of thermoplastic elastomer |
Publications (2)
Publication Number | Publication Date |
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EP0963383A1 EP0963383A1 (en) | 1999-12-15 |
EP0963383A4 true EP0963383A4 (en) | 2002-10-24 |
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Application Number | Title | Priority Date | Filing Date |
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EP19980907618 Withdrawn EP0963383A4 (en) | 1997-02-26 | 1998-02-25 | CROSSLINKING OF THERMOPLASTIC ELASTOMERS BY HYDROSILYLATION |
Country Status (12)
Country | Link |
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US (1) | US6251998B1 (xx) |
EP (1) | EP0963383A4 (xx) |
JP (1) | JP4610026B2 (xx) |
KR (1) | KR20000075698A (xx) |
CN (1) | CN1118484C (xx) |
AU (1) | AU726095B2 (xx) |
BR (1) | BR9807773A (xx) |
CA (1) | CA2281632A1 (xx) |
IL (1) | IL123470A0 (xx) |
MY (1) | MY117775A (xx) |
TW (1) | TW393500B (xx) |
WO (1) | WO1998038226A1 (xx) |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6150464A (en) * | 1995-12-01 | 2000-11-21 | Advanced Elastomer Systems, L.P. | Preferred process for silicon hydride addition and preferred degree of polymerization for silicon hydride for thermoplastic vulcanizates |
DE69915900T3 (de) † | 1998-01-20 | 2008-06-26 | Jsr Corp. | Thermoplastische Elastomerzusammensetzung |
US6206339B1 (en) | 1999-10-04 | 2001-03-27 | Illinois Tool Works Inc. | Rotary fuel filler valve actuator |
JP2001348464A (ja) * | 2000-06-07 | 2001-12-18 | Shin Etsu Polymer Co Ltd | 高分子系マトリックス、およびその製造方法 |
US6743862B2 (en) | 2000-06-20 | 2004-06-01 | Mitsui Chemicals, Inc. | Crosslinkable rubber compositions and uses thereof |
JP2002146133A (ja) * | 2000-11-16 | 2002-05-22 | Mitsui Chemicals Inc | オレフィン系熱可塑性エラストマー組成物およびその組成物からなる成形体 |
US6433090B1 (en) * | 2001-01-26 | 2002-08-13 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers having improved set foams made therefrom |
FR2829141B1 (fr) * | 2001-09-03 | 2006-12-15 | Nexans | Procede de fabrication d'un corps cylindrique et cable comportant un corps obtenu par ce procede |
WO2003059963A1 (en) * | 2002-01-15 | 2003-07-24 | Advanced Elastomer Systems, L.P. | Thermoplastic elastomers and process for making the same |
JP4111511B2 (ja) * | 2002-09-30 | 2008-07-02 | テクノポリマー株式会社 | ゴム強化ビニル系樹脂、ゴム強化ビニル系樹脂の製造方法、ゴム強化ビニル系樹脂組成物 |
AU2003304716A1 (en) | 2002-10-15 | 2005-11-25 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
JP4218342B2 (ja) * | 2002-12-27 | 2009-02-04 | Jsr株式会社 | オレフィン系熱可塑性エラストマーシートおよびその製造方法並びに積層体 |
US7439304B2 (en) * | 2004-06-03 | 2008-10-21 | Advanced Elastomer Systems, L.P. | Thermoplastic vulcanizates and process for making the same |
DE602004024215D1 (de) * | 2003-09-17 | 2009-12-31 | Exxonmobil Chem Patents Inc | Ellungsverfahren dafür |
US7015284B2 (en) | 2004-01-06 | 2006-03-21 | The Goodyear Tire & Rubber Company | Thermoplastic elastomer composition |
US7340280B2 (en) * | 2004-02-26 | 2008-03-04 | Nokia Corporation | Method of configuring base station, and base station |
US7365131B2 (en) * | 2004-04-28 | 2008-04-29 | The Goodyear Tire & Rubber Company | Thermoplastic vulcanizate composition |
US7326748B2 (en) * | 2004-06-14 | 2008-02-05 | The Goodyear Tire & Rubber Company | Thermoplastic composition |
EP1655330B1 (en) * | 2004-11-09 | 2008-03-19 | Advanced Elastomer Systems, L.P. | Soft thermoplastic vulcanizates from very low density polyethylene copolymers |
US7351774B2 (en) * | 2005-09-15 | 2008-04-01 | Michelin Recherche Et Technique S.A. | Silicon-modified crumb rubber composition |
US7312286B2 (en) * | 2005-12-02 | 2007-12-25 | Stockhausen, Inc. | Flexible superabsorbent binder polymer composition |
US7767743B2 (en) * | 2006-03-10 | 2010-08-03 | Exxonmobil Chemical Patents Inc. | Processable branched isoolefin-alkylstyrene elastomers |
US7951871B2 (en) * | 2006-11-10 | 2011-05-31 | Exxonmobil Chemical Patents Inc. | Curing rubber by hydrosilation |
WO2008134173A1 (en) * | 2007-05-01 | 2008-11-06 | Advanced Elastomer Systems, L.P. | Method for preparing thermoplastic vulcanizates |
US8969481B2 (en) | 2008-12-18 | 2015-03-03 | Exxonmobil Chemical Patent Inc. | Peroxide cured TPV |
US8247494B2 (en) * | 2009-11-23 | 2012-08-21 | Exxonmobil Chemical Patents Inc. | Thermoset compositions with dispersed thermoplastic resin therein and process for making them |
CN103459434B (zh) * | 2011-03-25 | 2016-05-11 | 埃克森美孚化学专利公司 | 乙烯基大分子单体使用茂金属的氢硅烷化 |
JP6257613B2 (ja) | 2012-06-29 | 2018-01-10 | ダウ グローバル テクノロジーズ エルエルシー | 熱可塑性加硫物のためのエチレン/αオレフィン/非共役ポリエン系組成物 |
EP2690136A1 (en) | 2012-07-25 | 2014-01-29 | Lanxess Elastomers B.V. | Thermoplastic elastomer compositions and process for preparing them |
BR112015010919B1 (pt) | 2012-11-30 | 2021-08-17 | Dow Global Technologies Llc | Composição, composição reticulada e artigo |
JP7381449B2 (ja) | 2017-08-24 | 2023-11-15 | ダウ グローバル テクノロジーズ エルエルシー | エチレン/c5-c10アルファ-オレフィン/ポリエチレンインターポリマー |
CN111032301A (zh) | 2017-08-31 | 2020-04-17 | 埃克森美孚化学专利公司 | 制备热塑性硫化胶(tpv)的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3881536A (en) * | 1972-08-31 | 1975-05-06 | Ppg Industries Inc | Rubber vulcanizates |
US4803244A (en) * | 1987-11-16 | 1989-02-07 | Union Carbide Corporation | Process for the preparation of thermoplastic elastomers |
EP0651009A1 (en) * | 1993-10-21 | 1995-05-03 | Sumitomo Bakelite Company Limited | Thermoplastic elastomer composition |
EP0776937A2 (en) * | 1995-12-01 | 1997-06-04 | Advanced Elastomer Systems, L.P. | Hydrosilylation crosslinking |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3037954A (en) * | 1958-12-15 | 1962-06-05 | Exxon Research Engineering Co | Process for preparing a vulcanized blend of crystalline polypropylene and chlorinated butyl rubber |
US4130535A (en) * | 1975-07-21 | 1978-12-19 | Monsanto Company | Thermoplastic vulcanizates of olefin rubber and polyolefin resin |
-
1998
- 1998-02-25 JP JP53779598A patent/JP4610026B2/ja not_active Expired - Lifetime
- 1998-02-25 EP EP19980907618 patent/EP0963383A4/en not_active Withdrawn
- 1998-02-25 US US09/367,484 patent/US6251998B1/en not_active Expired - Lifetime
- 1998-02-25 BR BR9807773-2A patent/BR9807773A/pt not_active Application Discontinuation
- 1998-02-25 KR KR1019997007765A patent/KR20000075698A/ko active IP Right Grant
- 1998-02-25 AU AU63380/98A patent/AU726095B2/en not_active Ceased
- 1998-02-25 CN CN98802831A patent/CN1118484C/zh not_active Expired - Fee Related
- 1998-02-25 CA CA002281632A patent/CA2281632A1/en not_active Abandoned
- 1998-02-25 MY MYPI98000827A patent/MY117775A/en unknown
- 1998-02-25 WO PCT/US1998/003645 patent/WO1998038226A1/en active IP Right Grant
- 1998-02-26 TW TW087102801A patent/TW393500B/zh not_active IP Right Cessation
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3881536A (en) * | 1972-08-31 | 1975-05-06 | Ppg Industries Inc | Rubber vulcanizates |
US4803244A (en) * | 1987-11-16 | 1989-02-07 | Union Carbide Corporation | Process for the preparation of thermoplastic elastomers |
EP0651009A1 (en) * | 1993-10-21 | 1995-05-03 | Sumitomo Bakelite Company Limited | Thermoplastic elastomer composition |
EP0776937A2 (en) * | 1995-12-01 | 1997-06-04 | Advanced Elastomer Systems, L.P. | Hydrosilylation crosslinking |
Non-Patent Citations (1)
Title |
---|
See also references of WO9838226A1 * |
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TW393500B (en) | 2000-06-11 |
JP4610026B2 (ja) | 2011-01-12 |
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BR9807773A (pt) | 2000-02-22 |
IL123470A0 (en) | 1998-09-24 |
CN1118484C (zh) | 2003-08-20 |
AU726095B2 (en) | 2000-11-02 |
CA2281632A1 (en) | 1998-09-03 |
US6251998B1 (en) | 2001-06-26 |
AU6338098A (en) | 1998-09-18 |
EP0963383A1 (en) | 1999-12-15 |
WO1998038226A1 (en) | 1998-09-03 |
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